Influence of primary ion species on the secondary cluster ion emission process from SAMs of hexadecanethiol on gold

In order to investigate the secondary cluster ion emission process of organo-metallic compounds under keV ion bombardment, self-assembled monolayers (SAMs) of alkanethiols on gold are ideal model systems. In this experimental study, we focussed on the influence of the primary ion species on the emission processes of gold-alkanethiolate cluster ions from a hexadecanethiol SAM on gold. For this purpose, we carried out time-of-flight secondary ion mass spectrometry (TOF-SIMS) measurements using the following primary ion species and acceleration voltages: Ar⁺, Xe⁺, SF₅⁺ (10 kV), Bi⁺, Bi₃⁺(25 kV), Bi₃²⁺, Bi₅²⁺, Bi₇²⁺ (25 kV).It is well known that molecular ions M⁻ and gold-alkanethiolate cluster ions Au_xM_y⁻ with M = S-(CH₂)₁₅-CH₃, x − 3 ≤ y ≤ x + 1, x, y > 0, show intense peaks in negative mass spectra. We derived yields Y_SI exemplarily for the molecular ions M⁻ and the gold-hexadecanethiolate cluster ions Au_y+1M_y⁻ up to y = 8 and found an exponentially decreasing behaviour for increasing y-values for the cluster ions.In contrast to the well-known increase in secondary ion yield for molecular secondary ions when moving from lighter to heavier (e.g. Ar⁺ to Xe⁺) or from monoatomic to polyatomic (e.g. Xe⁺ to SF₅⁺) primary ions, we find a distinctly different behaviour for the secondary cluster ions. For polyatomic primary ions, there is a decrease in secondary ion yield for the gold-hexadecanethiolate clusters whereas the relative decrease of the secondary ion yield ξ_Y with increasing y remains almost constant for all investigated primary ions.     

Resolution of a Coulomb reorientation ambiguity in 18O

Elastic scattering data and inelastic excitation of the lowest 2⁺ state in ¹⁸O from 120 MeV ¹⁸O incident on ²⁰⁸Pb are analyzed in coupled channels including couplings to the second 2⁺ state of ¹⁸O. This analysis favors the positive sign for the product of the four E2 matrix elements, p₄ = M₀₁₂₁,M₀₁₂₂M₂₁₂₂M₂₁₂₁ where M_ij = ?〈i∥M(E2)∥j〉. This is in agreement with shell-model calculations.     

Low-energy excited states of 3d transition metal ions in zinc selenide

The results of studying the impurity heat capacity of Zn_1?x M _xSe (M = Cr²⁺, Fe²⁺, Ni²⁺, Mn²⁺) solid solutions in the temperature range 1.8–20.0 K are presented. A heat-capacity method is described and applied for the measurement of the intracenter-transition energy in these systems. The role of the Jahn-Teller effect in the formation of low-energy excited states of 3d ions in ZnSe is discussed.     

Synthesis and physical properties of negative thermal expansion materials Zr1−xMxW2O8−y (M=Sc, In, Y) substituted for Zr(IV) sites by M(III) ions

Zr_1−xM_xW₂O_8−y (M=Sc, In and Y) solid solutions substituted up to x=0.04 for Zr(IV) sites by M(III) ions were synthesized by a solid-state reaction. X-ray diffraction experiments from 90 to 560 K revealed that all solid solutions had a cubic crystal structure and showed negative thermal expansion coefficients. The lattice parameters of Zr_1−xM_xW₂O_8−y were smaller than that of ZrW₂O₈ probably due to oxygen defects, though the ionic radii of substituted M³⁺ ions were larger than that of Zr⁴⁺. Order-disorder phase transition temperatures of the substituted samples drastically decreased in the order of Y, In and Sc compared to the percolation theory, and decreased with increasing M content.     

Estimation of T1 for Co2+ ions from temperature variation of the EPR linewidths for Gd3+ in Ce2Co3(NO3)12.24H2O single crystals

EPR of Gd³⁺ doped in Ce₂M″₃(NO₃)₁₂.24H₂O (M″ = Mg, Zn, Co) single crystals has been studied at various temperatures from room temperature to 77 K using ∼ 9.45 GHz EPR spectrometer. The observation of resolved Gd³⁺ spectra at room temperature in Ce₃Co₂(NO₃)₁₂.24H₂O has been interpreted in terms of a random modulation of the interaction between the Gd³⁺ and the Co²⁺ ions by the rapid spin-lattice relaxation of Co²⁺ ions. It is found that the effective spin-lattice relaxation time T₁ ∝ T⁻ⁿ where n = 1.85 (B∥z axis) and n = 1.75 (B⊥z axis) if 103 < T < 283 K.     

Magnetic resonance of the M x Mn1 ? x S compounds (M = Cu, Cr)

Cation-substituted manganese monosulfide M _x Mn_{1 ? x} S (M = Cu, Cr) has been investigated using the electron paramagnetic resonance method. The temperature and concentration dependences of the width and shape of the magnetic resonance line have been considered using the Van Vleck method of moments. It has been shown that, if the Mn²⁺ ions are substituted by the copper and chromium ions, the change of the effective exchange interaction in the system that substantially affects the magnetic resonance spectra takes place.     

Magnetic and dielectric properties of alkaline earth Ca and Ba ions co-doped BiFeO3 nanoparticles

Ca²⁺ and Ba²⁺ ions co-doped BiFeO₃ nanoparticles, Bi_0.8Ca_0.2−xBa_xFeO₃ (x=0-0.20), were prepared by a sol-gel method. The phase structure, grain size, dielectric and magnetic properties of the prepared samples were investigated. The results showed that the lattice structure of the nanoparticles transformed from rhombohedral (x=0) to orthorhombic (x=0.07-0.19) and then to tetragonal (x=0.20) with x increased. The dielectric properties of the nanoparticles were affected by the properties of the substitutional ions as well as the crystalline structure of the samples. The magnetic properties of the nanoparticles were greatly improved and the T_N of the nanoparticles was obviously increased. All the Ca²⁺ and Ba²⁺ ions co-doped BiFeO₃ nanoparticles presented the high ratio of M_r/M from 0.527 to 0.571 and large coercivity from 4.335 to 5.163 KOe.     

Anisotropy of hexagonal ferrites with M,W and Y structures containing Fe3+ and Fe2+ as magnetic ions

The ferrimagnetic saturation moment and hexagonal anisotropy constant K₁ have been measured at 4K on a Zn₂Y single crystal and on polycrystalline BaFe²⁺₂W and SrFe²⁺₂W samples. The moment of Fe₂W is in agreement with a collinear spin coupling and with the known site occupation for the Fe²⁺ ions. The moment of Zn₂Y is 9% lower than the value for a collinear configuration.The uniaxial anisotropy of Fe²⁺ in hexagonal ferrites is discussed and compared with that of Co²⁺. No noticeable Fe²⁺ anisotropy is found in Fe₂W in contrast to LaM = LaFe²⁺Fe³⁺₁₁O₁₉, in which the Fe²⁺ anisotropy is strong. The difference is attributed to the symmetry difference of the sites occupied by the Fe²⁺ ions in both compounds. The current theory does not satisfactorily explain the anisotropy and quadrupole splitting of Fe²⁺ in LaM. From this it is concluded that admixing of ⁵E states and (or) the influence of a dynamical Jahn-Teller effect cannot be neglected.The dipole-dipole anisotropy is computed for the M, W and Y structure and some deviation from the literature data is found. Using these results, a mean anisotropy of 1.3 to 2.3 cm^?1 per Fe³⁺ ion is found for the three structures.     

Magneto-crystalline properties of BaFe12−2x M x Sn x O19 (M = Sn, Ni, Zn) ferrite powders

BaFe_12?2x M _x Sn _x O₁₉ compounds, where M?=?Sn²⁺, Ni²⁺ or Zn²⁺ ions, were synthesized by mechanical milling and partially by citrate precursor methods. Analysis of magneto-crystalline structure has been carried out by Mössbauer spectroscopy. The Sn⁴⁺ ions replace Fe³⁺ ions on 2b and slightly on 2a?+?4f₁ sites, Zn²⁺ ions strongly prefer 4f₁ sites, Sn²⁺ ions prefer 4f₁ sites too and Ni²⁺ ions occupy 4f₂ and 12k or 2a sites. The magnetic properties were evaluated by the vibrating sample magnetometry and the thermomagnetic analysis. A large variation of the intrinsic coercivity H _c (330 to 78 kA/m) and of temperature coefficient of coercivity of ΔH _c /Δ? (0.39 to 0.22 kA/m°C) were achieved as a function of the (Zn–Sn) and (Sn–Sn) substitutions, respectively. The Curie temperature T _c decreased with the (Ni–Sn) substitution from 447 to 399°C.     

The tunable magnetic properties and microstructures of Co–Ni double-substituted M-type Casrla hexaferrites

M-type hexaferrites with Co²⁺ and Ni²⁺ions substituting for Fe³⁺ ions (Ca_0.30Sr_0.35La_0.35Fe_12.0−x(Co_0.5Ni_0.5)_xO₁₉, 0.0 ≤ x ≤ 1.0) were prepared by the traditional solid state method. X-ray diffractometer (XRD), field emission scanning electron microscopy (FE-SEM), physical property measurement system-vibrating sample magnetometer (PPMS-VSM) have been employed to study the microstructures and magnetic properties of hexaferrites. XRD patterns showed that the single magnetoplumbite phase is obtained if Co–Ni content (x) ≤ 0.4 and impurity phases are observed in the structure when Co–Ni content (x) ≥ 0.4. FE-SEM micrographs showed that the hexaferrites with hexagonal platelet-like grains is obtained. The saturation magnetization (M_s), remanent magnetization (M_r), M_r/M_s ratio, magneton number (n_B), coercivity (H_c), magnetic anisotropy field (H_a) and first anisotropy constant (K₁) decrease with increasing Co–Ni content (x) from 0.0 to 1.0. And our reported results with tunable H_c and M_r can be used for recording applications.     

Quadratic crystal field tensors and spin Hamiltonian tensors of Fe3+ in Li2Ge7O15 above and below the phase transition temperature

Dopant Fe³⁺ ions in tetrahedral and octahedral positions of Ge⁴⁺ in the crystal Li₂Ge₇O₁₅ were studied using EPR. Fe³⁺ substitutes for Ge⁴⁺ with a local charge compensation. The octahedral site and the tetrahedral sites significantly differ by the value of the invariant sumS(B ₄) of theB ₄ tensor of the spin Hamiltonian of Fe³⁺. The irreducible tensor products {V ₄ ? V ₄}₄ and {V ₄?V ₄}₂ theV ₄ tensor of the crystal field calculated using the point-charge model for octahedral and tetrahedral complexes provide the predominant contribution of the crystal field to theB ₄ andB ₂ tensors of the spin Hamiltonian of Fe³⁺, respectively. A comparison of the fourth-rank tensorsB ₄ of the spin Hamiltonian and {V ₄?V ₄}₄ of the crystal field determined at 300 K with those determined at 77 K supports the conclusion that the phase transition is accompanied by combined rotation of the [GeO₄] tetrahedra with the [Ge(1)O₆] octahedron almost unaltered. The spectrum lines are narrow and the variety of point defects in the vicinity of the paramagnetic impurity ions Fe³⁺, Cr³⁺ and Cu²⁺ is not detected. These facts are inconsistent with the statistically distributed model for the Li(2) atom. In specific cases at 300 K, when the wings of the two spectrum lines of theM→M+1 and theM+2 →M+3 transitions of Fe³⁺ ions belonging to one system of translationally equivalent positions overlap an extra line appears in the center between these lines. It is suggested that this effect is due to the soft phonon mode above the phase transition temperature.     

Propagation properties and M2 factors of a vortex Airy beam

We investigate the propagation properties and M² factor of a vortex Airy beam. The expression of M² factor as a function of the modulation parameters a_x and a_y is analytically obtained. The results indicate that the M² factor can achieve minimum M²=2.33 when a_x=a_y=1.026 for the m=1st order vortex Airy beam. For m=2, the M² factor can achieve minimum M²=7.53 when a_x=1.601 and a_y=0.529 (or a_y=1.601 and a_x=0.529). These results indicate that the far field divergence of the beam width in the sense of root-mean-square beam is related to modulation parameters a_x and a_y, and increases with increasing vortex order. Numerical calculations provide an intuitive physical picture for the effect of the modulation parameters on the propagation of the vortex Airy beam.     

Thiolated cyclodextrin self-assembled monolayer-like characterized with secondary ion mass spectrometry

In the work the focus is on the preparation of self-assembled monolayer-like films consisting of thiolated cyclodextrin on gold substrate and a characterization by using secondary ion mass spectrometry. The short (1 min) and long (1 h) time preparations of self-assembled monolayer-like films, resulting in submonolayer and monolayer regimes, are investigated, respectively. The observed species of thiolated cyclodextrin (M as molecular ion) self-assembled monolayer-like films are assigned to three groups: Au_xH_yS_z clusters, fragments with origin in cyclodextrin molecule associated with Au, and molecular ions. The group of Au_xH_yS_z (x = 2-17, y = 0-2, z = 1-5) clusters have higher intensities than other species in the positive and even more in negative mass spectra. Interestingly, the dependence between the number of Au and S atoms shows that with the increasing size of Au_xH_yS_z clusters up to 11 Au atoms, the number of associated S atoms is also increasing and then decreasing. Molecular species as (M−S+H)Na⁺, (M+H)Na⁺, AuMNa⁺, (M₂−S)Na⁺, and M₂Na⁺ are determined, and also in cationized forms with K⁺. The intensities of thiolated cyclodextrin fragments at the long time preparation are approximately 10 times higher than the intensities of the same fragments observed at the short time. The largest observed ions in thiolated cyclodextrin self-assembled monolayer-like films are AuM₂ and Au₂M. The thiolated cyclodextrin molecular ions are compared with hexadecanethiol molecular ions in the form of Au_xM_w where the values of x and w are smaller for thiolated cyclodextrin than for hexadecanethiol. This result is supported with larger, more compact, and more stabile thiolated cyclodextrin molecule.     

Noninversive partial velocity amplification of radiation by ions due to their rotation in a magnetic field

It is shown that upon the application of an external magnetic field, a gas of ionized particles may experience noninversive partial velocity amplification of radiation by ions due to their Larmor rotation. In this case, virtually all ions may be in the ground state. It may happen that approximately half the number of ions in the medium amplify the incident radiation. The integrated absorption coefficient remains positive due to the enhancement of absorption of radiation by the other half of ions. Noninversive amplification of radiation takes place when the condition ω_c?Γ²/kv _T is satisfied ωw_c is the cyclotron frequency of ions in the magnetic field; Γ is the homogeneous half-width of the absorption line for ions, and kv _T is the Doppler width). In the case of interaction of atomic ions with radiation in the optical range, this corresponds to magnetic fields B?600 G (for the ion mass M～10 amu). Noninversive partial velocity amplification of radiation is a “latent” effect in the sense that it disappears upon averaging over all velocity directions of ions. This effect is associated with the emergence of phase incursion of the induced dipole moment oscillations for ions moving in circular cyclotron orbits, which depends on the ion velocity.     

Improvement to the exchange field acting upon Tb ions in TbIG

The spin fluctuations of the magnetic ions play an important role on the magnetic properties of the crystals and lead to a new mechanism for the Curie-Weiss susceptibility. The exchange field H_exch acting on the rare-earth ions in Tb:YIG is improved based on the temperature dependence of the spin fluctuations, which is expressed as H_exch=n₀(1+γT+βT⁻²)M_YIG. By means of the improved exchange field, the magnetic and magneto-optical properties of Tb³⁺ ions in Tb:YIG are calculated. The calculated results are in good agreement with the measured data in the temperature range from 40 to 300 K.     

Influence of photoexcitation on the EPR spectra of Mo5+ in Li2Zn2(MoO4)3: Ce3+,Cu2+ crystals annealed in a CO2 atmosphere

The influence of recovery annealing in a CO₂ atmosphere at 700°C on the properties of Li₂Zn₂(MoO₄)₃ crystals doped with cerium and copper ions has been studied. The EPR investigation of Li₂Zn₂(MoO₄)₃ crystals annealed in a CO₂ atmosphere has revealed that the annealing leads to the formation of oxygen vacancies in positions adjacent to the oxygen octahedron of lithium, M3, and the oxygen tetrahedron of molybdenum, Mo1. In this case, the charge state of molybdenum becomes Mo⁵⁺ and appears in the EPR spectra in the form of one magnetically nonequivalent position. The analysis of the angular dependence of the EPR spectrum of Mo⁵⁺ made it possible to calculate the spectral parameters g _∥ = 1.862, g _⊥ = 1.933, A _∥ = 71.8 G, and A _⊥ = 34.1 G. The cross relaxation on the hyperfine structure from the molybdenum isotope ⁹⁷Mo is found in the EPR spectra. The photoexcitation of Li₂Zn₂(MoO₄)₃ crystal doped with cerium ions leads to the saturation of the EPR spectrum of Mo⁵⁺ and to the formation of the hyperfine structure from one lithium ion with a hyperfine structure constant of 14 G. For Li₂Zn₂(MoO₄)₃ crystals doped with copper ions, a very weak EPR spectrum of Mo⁵⁺ is observed in the initial crystals. As a result of the photoexcitation, an increase in the intensity of this spectrum by an order of magnitude and manifestation of the EPR spectrum of Cu²⁺ ions take place. It is assumed that such a behavior of the EPR spectra of molybdenum ions in Li₂Zn₂(MoO₄)₃ crystals doped with cerium and copper ions under photoexcitation is caused by different positions of the energy levels of cerium and copper ions with respect to the energy level of the molybdenum ion.     

An evidence for a possible stable dibaryon

A search for stableH-dibaryon ofI=0,Y=0,J ^P =0⁺ was undertaken in negative pion-, neutron-,¹²C-nucleus- and proton-propane interactions at 4.0, 7.0, 50.4 and 10 GeV/c, respectively, using 55 cm and 2 m propane bubble chambers. This technique permite one to examine the whole range of possibleH-mass value. In the range ofM _H >2M _Λ=2231.2 MeV/c² an enhancement ofM _ΛΛ=(2365.3±9.6) MeV/c², Γ _ΛΛ =(47.2±15.1) MeV/c² with production cross section σ=(24.2±7.0) μb per carbon nucleus was found. The mass rangeM _Σ?p<M _H <2M _Λ was explored via the search for a weak decay modeH→Σ^?+p. AV ⁰-particle was found pointing to a two-prong interaction and satisfying the kinematics of the above two-body decay mode with a high confidence level. The possibility of imitation of the observed event by background processes was investigated for a series of two-step strong reactions and weak decays. We succeeded to show the significance of theH-production hypothesis on a deuteron-mass nuclear fluctuon via thepd→HpK ⁺ K ⁰ reaction. The mass of the event treated as aH→Σ^?+p weak decay appeared to be (2173.94±1.32) MeV/c², its life-time being 0.668·10^?10 s. Both are in agreement with predictions of the MIT Bag Model for the so-calledH-dihyperon. The formally determined production cross section of theH in proton-propane interactions at 10 GeV/c is estimated to be 40 nb. Perhaps, this event can be considered as a first evidence for a six-quark bound state-H-dihyperon. An independent way for the search for theH-particle, based on a specific conversion processHN→YYN, peculiar to its intranuclear strong interactions was proposed and tried. For this purpose all events with two Λ-hyperons and identified protons were tested for the hypothesesH _p →ΛΛp at three fixed masses:M _H =1880.00, 2173.94 MeV/c² and the ΛΛ invariant mass for the event in question. The kinematics of this reaction fits successfully only one event and only atM _H =2173.94 MeV/c². It seems worthy of note that the final state ΛΛ invariant massM _ΛΛ=2344 MeV/c² is rather close to the observed peak at 2365 MeV/c². It is shown that the intranuclear conversion processes Ξ^? p→ΛΛ and Ξ⁰ n→ΛΛ fail to imitate the observed event. The ΛΛp invariant mass of this event equal to 3363 MeV/c² is out of a 3568 MeV/c² peak region of the ΛΛp invariant mass spectrum observed earlier. TheH conversion cross section exceeds the production one. Thus, we consider this event as providing a new evidence for the stableH-dibaryon ofM _H =(2173.94±1.32) MeV/c².     

A theoretical study of alkaline-earth cations in crystalline sodium chloride,potassium chloride and potassium bromide

Theoretical methods, based on Mott-Littleton techniques are used to investigate the defect structures of alkali-halide crystals doped with divalent ions. The systems studied are those having Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺ as impurity ions in NaCl, KCl and KBr crystals. Our calculations find comparable stability of the (110) nearest-neighbour and (200) next-nearest-neighbour complexes whereas the (211) complex is found to be less stable. Significant trends in the variation of binding energy with dopant ion radius are predicted. We also consider the activation energies for the w₁, w₂, w₃ and w₄ type jumps which occur in the vicinity of the impurity ion. The results are, where possible, compared with experimentally determined defect energies and their implications in diffusion processes of M²⁺ impurities in the alkali halides are discussed.     

Elucidation of Selectivity for Uranyl Ions with an ICT Organosilane-Modified Fluorescent Receptor

A fluorescent receptor, isocyanatopropyl trimethoxysilane grafted 9-amino acridine (AcI), was synthesized and characterized by elemental analysis, FTIR and NMR spectroscopy. Photophysical properties and pH-dependent fluorescence behavior of AcI were investigated and its complex stoichiometry with uranyl ion was elucidated. Change in fluorescence emission of AcI with pH of the solution was observed and pKa value was determined by using integrated emission intensity versus pH. It was found that AcI exhibited fluorescence enhancement, which can be attributed to an internal charge transfer (ICT) mechanism, upon titration with uranyl ions in mixture of ethanol-buffer solution while the fluorescence emission of AcI was not affected by addition of other divalent transition metal ions except mercury (II) ions. On the other hand, the both fluorescence and UV-vis titration measurements revealed unique selectivity for uranyl ions over the interfering mercury (II) ions. The spectrofluorometric titration clarified that uranyl interacted with AcI to form AcI ₂(UO ₂ ^2?+ )₃ (2:3) complex structure with an apparent association constant of K?=?7.41?×?10⁶ M^?2/3. The interference effect of some cations on fluorescence enhancement exhibited by complex was also tested.     

Brownian motion on a manifold as a limit of Brownian motions with drift

Let ?ⁿ be n-dimensional Euclidean space and let M ? ?ⁿ be a smooth compact m-dimensional Riemannian manifold (without boundary) embedded in ?ⁿ. By a Brownian motion on M we mean a Markovian process whose transition semigroup is defined by the generator ?½Δ_M, where Δ_M stands for the Laplace-Beltrami operator on M (see, e.g., [2]). This note extends a series of papers in which a measure generated by a Brownian motion on M on the space of trajectories (with values in M) can be represented as the weak limit of measures on the space of trajectories in the ambient space ?ⁿ (see [7–10]). Namely, we claim that a sequence of diffusion processes on ?n which are Brownian motions with drift (in the direction of the manifold) with infinitely increasing modulus converges in distribution to a Brownian motion on the manifold.